Der Mechanismus der Addition von Nucleophilen an Alkinderivate mit Push-pull-Gruppen

The mechanism of the addition of nucleophiles to alkyne-derivatives 1 having both push- and pull-groups yielding Michael-adducts is investigated. The rate of the second-orderreaction increases (a) with increasing nucleophilic character of the amine and alcohol respectively, (b) with increasing electrophilic character of the alkyne-derivatives 1 , and (c) with increasing solvent polarity. These results support as rate-determining step an attack of the nucleophile at C(3) of the alkyne-derivatives.     

Versuche zur Synthese von Calicen aus trisubstituierten Cyclopropanen und Cyclopentenon

Attempted Synthesis of Calicene from Trisubstitued Cyclopropanes and Cyclopentenone The Li carbenoids 4 , prepared by treatment of substituted 1,1-dihalocyclopropanes with BuLi, are reacted with cyclopent-2-enone under thermodynamic and kinetic control (Scheme 1). In general, the latter procedure gives better yields of cyclopropylcyclopentenols 5a – e , but the reaction seems to be controlled mainly by the steric and electronic properties of the substituent Y. So, with 4b and 4e , the main reaction is the attack of the carbenoid at C(1) of cyclopent-2-enone, while 4a (Y = PhS) predominantly deprotonates the ketone (Scheme 4). Whereas 5d and 5e can easily be converted to the dihydrocalicenes 6d and 6e (Scheme 6), the attempted elimination of H₂O from 5a – c leads to the rearranged products 13 – 2 due to the opening of the cyclopropane ring (Scheme 5). Finally, the generation of the parent compound 2 from the silylated precursor 6d is attempted: treatment with MeO^? gives the addition products 18A/18B , while the reaction with Br₂ provides 19 by a bromination/dehydrobromination sequence (Scheme 7).     

3J(H,H) Coupling Constants as a Simple Criterion for π Delocalization of Pentafulvenes and Pentafulvalenes

A simple criterion for estimating the extent of π delocalization in the five-membered ring of pentafulvenes and pentafulvalenes is described. It is based on the fact that changes of bond lengths (induced by exocyclic substituents R¹-R² of 1 ) are reflected by systematic changes of ³J(H,H) values, so that linear correlations of σ vs, ³J(H,H)are obtained. Plots of that type (Fig. 1) are very useful for determining the extent of π delocalization of various pentafulvalenes 2 – 5 (Fig. 3) which show a very similar behavior to pentafulvenes. In principle, these plots could additionally be used for estimating substituent constants σ or for approximating the extent of π overlap between exocyclic substituents and the π system of pentafulvenes. Charge-density effects of pentafulvenes and pentafulvalenes are observed by substituen-induced shifts of the ring C-atoms (Fig. 4).     

Die 1,3-dipolare Cycloaddition von Acetylendicarbonsäure-estern an 2-Methyl-4-phenyl-chinazolin-3-oxid

The 1,3-dipolar addition of acetylenedicarboxylic esters (IX and X) to 2-methyl-4-phenyl-quinazoline 3-oxide (VIII) in benzene/methanol and benzene/ethanol, respectively, gives the esters XI and XII of 3-amino-3-phenyl-2-(2-acetamidophenyl)-acrylic acid as main products and the esters XIII and XIV of 2-methyl-4-phenyl-5H-benzo[d][1,3]diazepin-5-carboxylic acid as by-products. The constitutions of XI and XII are elucidated by acid hydrolysis to the 2-phenylindole-3-carboxylic esters VI and VII, respectively, and by ozonolysis of XII to give benzamide and ethyl o-acetamido-mandelate (IV). The alkaline hydrolysis of XI or XII gives the enamine derivative XVIII, which is hydrolysed by acid to oxindole and benzoic acid. The structure elucidation of XIII and XIV is based on spectroscopic data together with thc formation of XV by alkaline hydrolysis. Mechanisms arc proposed for the reaction paths.     

Synthese und NMR-Spektren von Nonafulven sowie Vergleich mit 10-Phenylnonafulven

Synthesis and NMR Spectra of Nonafulvene and Comparison with 10-Phenylnonafulvene Experimental procedures for the reaction of cis,cis,cis,trans-cyclononatetraenide (ccct-CNT^?; see 4 ) with bromomethyl acetate ( 1a , R = H, X = Br) to give (cyclononatetraenyl)methyl acetate ( 5a ; 84% yield) as well as for the base-induced elimination of HOAc from 5a to give nonafulvene ( 6a ; 44% yield) are described. Spectroscopic as well as chemical evidence for 6a and 6b is presented. An approximate high-field-NMR analysis of 6a and 6b has been completed. The results are in favour of a fast interconversion of the type 6A?6B (Scheme 4), and supported by the MNDO-optimised geometry of 6a . The first X-ray analysis of a cyclononatetraene (i.e. of 5b ) has been accomplished: 5b is a polyolefinic molecule with largely alternating bond lengths and with a nine-membered ring deviating strongly from planarity.     

1H- and 13C-NMR Investigation of Nonafulvenes

¹H- and ¹³C-NMR spectra of a series of nonafulvenes 1 have been investigated. Most nonafulvenes are olefinic molecules with alternating bond lengths, their nine-membered ring deviating strongly from planarity. The 10-monosubstituted nonafulvenes contain 2 sterically different ring segments with a nearly planar (E)-diene system consisting of C(7), C(8), C(9), C(10), and R. Substituents R are influencing C(9) > C(7) > C(5). In symmetrically substituted nonafulvenes a fast process equilibrating olefinic conformers is operating so that pairs of ring protons and ring C-atoms are equivalent and only average substituent effects are observed for C(9) > C(7,2). ¹H- and ¹³C-NMR chemical shifts are not significantly influenced by changes of solvent or temperature. On the other hand, new ¹³C- and ¹H-NMR experiments completing previous investigations by Hafner and Tappe confirm that NMR spectra of 10,10-bis (dialkylamino)nonafulvenes are strongly dependent on solvent polarity and temperature. At ambient temperature and in unpolar solvents, nonplanar conformers are predominant, their spectral data fitting into the series of other nonafulvenes. At low temperature and/or in polar solvents, dipolar conformers are favoured which are characterised by charge separation and a planarised (but not necessarily completely planar) nine-membered ring with negative excess charge. The spectroscopic behaviour of nonafulvenes is reasonably explained by a qualitative scheme (Fig. 7) which is based on a model proposed by Boche for nonafulvenolates.     

Synthese von ‘Push-Pull’-Oligoacetylenen

Synthesis of ‘Push-Pull’-OligoAcetylenes ‘Push-pull’ triacetylenes 11a , b , c , as well as ‘push-pull’ tetraacetylene 13b have been prepared by reaction of the corresponding trichloroene(oligoinyl)amines 9 and 10 with 2 mol-equiv. of BuLi followed by acylation. The sequences (Schemes 3 and 4) are very simple and straightforward, they could in principle be applied to the synthesis of ‘push-pull’ pentaAcetylenes 15 and hexaacetylenes 17 (Scheme 5). Main limitations are the moderate yields as well as the low thermal stability of push-pull oligoacetylenes.     

«Push-Pull»-Acetylene als Hilfsmittel zur Synthese von Peptiden

Peptide synthesis by Means of ‘Push-Pull’-Acetylenes ‘Push-pull’-acetylenes 1 are excellent reagents for peptide synthesis: Addition of ‘push-pull’-acetylenes to solutions of N-protected amino acids (or vice versa) gives enol esters 5 , which react selectively with the amino function of a second amino acid. In this way serine, tyrosine, 4-hydroxyproline, cysteine as well as histidine are linked to form dipeptide esters without protection of the second functional group (OH, SH or NH). The amount of racemization is very low. Similarly tri- as well as tetrapeptides are available. The versatility of the reaction is discussed.     

A gaussian central limit theorem for trimmed products on simply connected step 2-Nilpotent Lie groups

A limit theorem due to J. Kuelbs and M. Ledoux, valid for dilatation-stable laws on type 2-Banach spaces, is carried over to stable laws on simply connected step 2-nilpotent Lie groupsG. We show that for products of i.i.d. random variables in the of attraction of a nondegenerate semigroup onG, where is a one-parameter automorphism group acting contracting onG, a certain intermediate trimming procedure, together with a suitable norming, always yields a nondegenerate centered Gaussian limit.     

Low‐Temperature Olefin Syntheses in View of Parent Fulvenes and Fulvalenes

Parent fulvenes and fulvalenes are thermally unstable cross‐conjugated olefins for which low‐temperature syntheses are indispensable. In this review 5 syntheses (in the temperature range between ?100 and ?10°) are discussed: 1. Reaction of sodium cyclopentadienide with 1‐acetoxy‐1‐chloroalkanes or 1‐acetoxy‐1‐bromoalkanes ( 26 ) gives acetoxy‐alkyl‐cyclopentadienes ( 27 ) which are easily converted to pentafulvenes ( 2 ) by low‐temperature HOAc‐elimination with NEt₃. This synthesis has been applied to parent pentafulvene ( 2a ), heptafulvene ( 3a ), nonafulvene ( 4a ) and sesquifulvalene ( 19a ) (Schemes 8–11). 2. Based on a nearly quantitative oxidative coupling of cyclononatetraenide ( 8 ) to give dihydrononafulvalene ( 38 ) (Scheme 10), a general synthetic plan for fulvalenes has been outlined (Scheme 11) and applied to the synthesis of pentafulvalene ( 12 ), nonapentafulvalene ( 16 ) and nonafulvalene ( 14 ). Several applications of oxidative couplings of Hückel anions are discussed (Schemes 20 and 21). 3. Trifunctional cyclopropanes 67 (in most cases 1,1‐dibromo‐2‐X‐cyclopropanes) are attractive precursors of parent triafulvene ( 1a ) and calicene ( 17 ) (Scheme 18). Contrary to classical procedures they are transformed into nucleophiles ( 67 → 68 ) by halogen‐lithium exchange, methylation ( 68 → 69 ) and HBr‐elimination to give 1‐methylidene‐2‐X‐cyclopropanes of type 71 . By subsequent HX‐elimination triafulvene ( 1a ) has been synthesized and trapped as a [4+2]‐cycloadduct 73 (Scheme 20). Furthermore, calicene precursors 77 are available by using cyclopentenone as an electrophilic cyclopentadiene equivalent. 4. Similarly, 1‐lithio‐1‐bromo‐2‐X‐cyclopropanes 68 are directly transformed into triafulvalene precursors 81 (Scheme 26) by a novel CuCl₂‐catalyzed oxidative coupling. 5. In view of the synthesis of parent triafulvene ( 1a ), triafulvalene ( 11 ) and calicene ( 17 ), retro‐Diels? Alder reactions of stable precursors – prepared by low‐temperature reactions (described in chapters 3 and 4 ) – have been explored.